CN104350420B - For handling the manufacturing method of monomolecular equipment - Google Patents
For handling the manufacturing method of monomolecular equipment Download PDFInfo
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- CN104350420B CN104350420B CN201380026733.6A CN201380026733A CN104350420B CN 104350420 B CN104350420 B CN 104350420B CN 201380026733 A CN201380026733 A CN 201380026733A CN 104350420 B CN104350420 B CN 104350420B
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Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/48—Biological material, e.g. blood, urine; Haemocytometers
- G01N33/483—Physical analysis of biological material
- G01N33/487—Physical analysis of biological material of liquid biological material
- G01N33/48707—Physical analysis of biological material of liquid biological material by electrical means
- G01N33/48721—Investigating individual macromolecules, e.g. by translocation through nanopores
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
- B81C1/00—Manufacture or treatment of devices or systems in or on a substrate
- B81C1/00015—Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems
- B81C1/00023—Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems without movable or flexible elements
- B81C1/00087—Holes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0002—Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
- B81C2201/00—Manufacture or treatment of microstructural devices or systems
- B81C2201/01—Manufacture or treatment of microstructural devices or systems in or on a substrate
- B81C2201/0101—Shaping material; Structuring the bulk substrate or layers on the substrate; Film patterning
- B81C2201/0147—Film patterning
- B81C2201/0149—Forming nanoscale microstructures using auto-arranging or self-assembling material
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biomedical Technology (AREA)
- Nanotechnology (AREA)
- General Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Biophysics (AREA)
- Molecular Biology (AREA)
- Food Science & Technology (AREA)
- Medicinal Chemistry (AREA)
- Hematology (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Urology & Nephrology (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Composite Materials (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Micromachines (AREA)
- Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Measuring Or Testing Involving Enzymes Or Micro-Organisms (AREA)
Abstract
The present invention relates to a kind of methods for manufacturing for handling monomolecular equipment.According to the method, self assembly resist (155) is deposited on process layer (110, PL), and it is allowed to be self-assembled into the pattern with two-phase (155a, 155b).Then one (155a) in the two phases is selectively removed, and at least one hole is generated in process layer (110, PL) by the exposure mask of remaining resist (155b).Therefore, the hole of small size can be readily produced, which allows to handle unimolecule (M), such as handles in DNA sequencing.
Description
Invention field
It can be used for handling the method for monomolecular equipment for manufacturing the present invention relates to a kind of.
Background technique
2010/0327847 Al of US discloses a kind of solid-state molecular sensor with a hole, and the hole extends
Across graphene layer.When molecule passes through the hole, the electrical characteristics for measuring the layer change.One of this sensor the disadvantage is that
The high conductivity of graphene layer, in contrast, as caused by molecule conduction sexually revise it is very small.
In addition, in document (H.W.Ch.Postma, " Rapid sequencing of individual DNA
Molecules in graphene nanogaps ", Nano Lett.10 (2010) 420-425) in described, can be by making
It is sequenced in gap of the DNA molecular across two graphene layers.However, when using free graphene layer, phase
Associated equipment is not mechanically very firm.In addition, the relatively long gap between the layer allows long molecule to pass through, it is described
Molecule has many different orientations and configuration, so that the interpretation of measurement result is highly difficult.
Summary of the invention
The object of the present invention is to provide improvement for handling monomolecular device, in particular for nucleic acid (such as DNA)
Sequencing device.
This purpose is realized by the manufacturing method according to claim 1 and equipment according to claim 14
's.Preferred embodiment is disclosed in dependent claims.
According to the method for the present invention for manufacturing a kind of equipment, wherein it is (or former to handle individual molecule by the equipment
Son), the especially macromolecular of such as protein or nucleic acid.Term " nucleic acid " in this background should most generally include
Molecule (for example, DNA, RNA) and LNA containing naturally occurring and/or non-naturally occurring nucleotide or its modification
(lock nucleic acid) and PNA (peptide nucleic acid).The processing of these molecules may include that it physically and/or chemically converts or change.However,
In many important applications, the processing will be sensing, specifically be used for the different sections of detection molecules.Therefore, citing comes
It says, may be that ss-DNA, ds-DNA etc. are sequenced.
The manufacturing method includes the following steps, the step is preferably executed with cited sequence, but can also be with
It is executed by any other appropriate sequence：
A) (solid-state) material layer is provided.For reference purposes, hereinafter, this layer will be referred to as " process layer " (table
Show that it is further processed in manufacturing process, and it participates in the unimolecule processing in the equipment realized).
The process layer optionally includes by two or more of different materials and/or structure composition sublayer.In addition,
The process layer can be homogeneous or (for example, geometric form or chemically) tool is structured.It, should as represented by term " layer "
Process layer will usually have laminar geometry, have sizable width and length compared with its thickness.
B) material is deposited on aforementioned processing layer (that is, on its outer surface), wherein the material there should be certain spy
Sign is to be self-assembled into the pattern being made of (at least) two different zones that there are different (chemistry and/or physics) to form, and its
In at least one of these regions can be selectively removed.Due to these attributes, the material will hereinafter be claimed
For " self assembly resist ".In addition, having the region of specific composition by " phase " of referred to as self assembly resist, that is to say, that
The resist is assembled into different at least two out of phase patterns (saying from meaning of the present invention), described at least two
At least one of phase can be selectively removed.After self assembly resist deposition, it is allowed to be self-assembled into its phase
Associated phase pattern.
C) the one (at least) phase for selectively removing aforementioned self assembly resist, leaves the pattern of another phase composition.
For example, the removal can be completed by selective etch.
D) by the exposure mask provided by remaining self assembly resist, at least one hole is generated in the process layer,
Wherein the hole makes it that unimolecule be allowed to pass through realized equipment.For example, the hole can be by with etching
Agent etches the process layer and generates, and the etchant will not influence the remaining phase of self assembly resist.
The method has following advantages, allows to generate small hole, can reliably be handled by the small hole
Unimolecule.This is to be realized by developing the self assembly characteristic of certain resists with the structure for generating nano-scale, described to receive
The structure of meter ruler cun is appropriate for desired purpose.Meanwhile the manufacturing method allows to produce in batches, because can be with this
The a large amount of holes of mode parallel production.For the production method of such as electron beam lithography, this is considerably advantageous, because passing through
These production methods can only sequentially produce the hole of smaller size.
After generating at least one described hole in process layer, the covering there are still self assembly resist in process layer
Film.According to one embodiment of present invention, this remaining resist remains in original place, as being (for example) electrically insulated.According to this hair
Bright another embodiment, the manufacturing method include the steps that additional " e) "：It is anti-that remaining self assembly is removed from the process layer
Lose agent.In this case, during the production of equipment, the self assembly resist is used only as reticule.
The process layer can optionally be pre-processed before the deposition of the self assembly resist in step b), and wherein this is pre-
Processing is so that it influences the resulting phase pattern formed by self assembly resist.Therefore, the formation of pattern can be controlled optionally
Or adjustment.
For example, aforementioned pretreatment may include that specific (by optionally structuring) surface is provided for the process layer
Chemically.According to preferred embodiment, the pretreatment of process layer includes depositing to resist in process layer and this resist
Patterning.For reference purposes, hereinafter, this resist will be referred to as " main resist ".By main resist
Patterning can generate the confined area for being (for example) similar to groove or hole on the surface of process layer, and self assembly resist can
Specific phase pattern is developed into the confined area.Therefore, the main resist may be used as described in a kind of be used for from group
Fill the frame or matrix of resist.
The preceding patterning of the main resist can complete especially by optical lithography and/or electron beam lithography.Light
It learns photoetching and advantageouslys allow for the parallel processing for realizing large area in one step, to provide coarse grained texture, self assembly for it
Fine structure can be added on the coarse grained texture by resist later.
Further exploitation according to the present invention, step b), c) and d)-the namely deposition of self assembly resist, this primary antibody
The generation-of the removal and at least one hole of losing a phase of agent can be executed relative to the first process layer for the first time, and the
Secondary phase for second processing layer execute, wherein first and second process layer can be it is identical or different.Optionally,
Can repeat other correlation steps, for example, remaining self assembly resist removal and/or (structuring) main resist deposition.
When executing the processing step to same process layer, this will lead to the difference figure according to the two kinds of self assembly resists applied
Case and generate hole in said layer.When executing the processing step to different process layers, resulting hole will be located at not
In same layer, and can also optionally have different pattern.
In previous embodiment in the specific implementation, second processing layer includes the first process layer.This hole that later period is generated
Gap also by penetrate included produced hole for the first time the first process layer.
In another realization of above-described embodiment, there may be by new material layer depositions to the first process layer (its
In step a)-d for the first time) in be structured) on other intermediate steps, wherein this new layer is by later in secondary step
Rapid b)-d) in the second processing layer that is structured include.
The pattern for the self assembly resist applied in the first time of abovementioned steps executes and second executes is preferably
It is different in terms of alignment thereof and/or geometry.This allows to generate complicated pore structure.
According to the preferred implementation of previous embodiment, the first and second patterns each include one (at least) phase composition
Striped, wherein the striped of the different pattern is angled with respect to each other.Then the hole generated by the self assembly resist
It will be inclined slit.Preferably, the inclined slit is in different layers and stacked on top of each other, therefore usually stacked at it
Smaller hole is formed in region.
It in general, may include by the striped or circle of a phase composition by the pattern of self assembly resist mutually generated
Cylinder.Striped allows to generate groove, and cylindrical body to generate circular hole in process layer.
In another preferred embodiment of the invention, self assembly resist may include block copolymer.Self assembly is against corrosion
The macromolecular of agent is then by two (or more) monomer compositions, wherein being made of the section of only one kind of monomer composition " embedding
Section ", and wherein different blocks alternates.By properly selecting monomer, corresponding block will have specified chemical and/or
Physical attribute, so that macromolecular (certainly) is arranged in specific pattern.
The process layer can specifically include non-conducting sublayer or material, such as SiO2、SiOxOr h-BN.As supplement
Or alternatively, the process layer may include conductive seed layer or material.
Aforesaid conductive sublayer or material can specifically include graphene, or the material as derived from graphene, such as graphite
Alkynes (referring to D.Malko, C.Neiss, F.Vinesc and A.Gorling, Phys Rev.Lett.108,086804 (2012)).By
In graphene in the advantageous electrically and mechanically attribute of nano-scale dimension, graphene (or derivative) is a kind of preferred material.Stone
Black alkene (or derivatives thereof) can reside in five or less nanometer layers, preferably in two nanometer layers, or it is more excellent
Selection of land is in a nanometer layer.Therefore, it can be achieved that advantageous relatively small thickness.
Additional layer can be at least partially deposited in the process layer by another exploitation according to the present invention, wherein
The additional layer can be specifically conductibility or non-conducting layer.Additional layer can be advantageous, because it increases machine
Tool stability provides electrical isolation (if it is non-conductive), and helps to take treated unimolecule suitably
To.In addition, additional layer can form another process layer, Huo Zheqi in the another application of structuring step of the invention
A part.
Depending on the monomolecular expected processing, it may be necessary to the additional components of the equipment.This base part can have
Body realizes that the circuit is suitable for controlling the reciprocation with the molecule for passing through the hole by circuit.This circuit is preferably
It is connected to process layer and/or its sublayer.In addition, the hole can be embedded into microfluidic circuit, it is ensured that by molecule of interest
(for example, DNA fragmentation) is sent to hole.
In a preferred embodiment, aforementioned circuit may be adapted to sense conductibility variation, and the sensitivities variation occurs
When the different piece of molecule or molecule passes through the hole.It therefore, for example, can be by detecting wearing across the hole
The sequencing of ss-DNA is realized in the appearance (this should depend on base) of tunnel electric current.
In order to allow the multiple unimolecules of parallel processing, it is preferable to provide multiple holes.Preferably, these holes are set to logical
With on carrier or substrate/in.The invention also includes one kind for handling monomolecular equipment, wherein the equipment can be by above-mentioned
Any method obtains.This means that the equipment can be produced by following step：
(a) provide " process layer ", (b) self assembly resist is deposited in the process layer, and make its be self-assembled by
The pattern of two phase compositions (c) selectively removes a phase of the self assembly resist, and (d) by it is remaining from
The exposure mask of assembling resist generates at least one hole in the process layer.Other manufacturing methods for the equipment include
Hole is (for example) generated by electron beam lithography.
According to preferred embodiment, aforementioned device may include：
A) with the bottom of the first hole, first hole is, for example, slit or preferably hole.Described first
Hole can pass through the method (that is, by applying self assembly resist) of the type described above or any other method next life
It produces.The bottom can be specifically non-conducting substrate.
B) conductive top layer is deposited on the bottom and has the second hole being set to above first hole,
To provide the hole that unimolecule may pass through jointly, wherein the top layer is divided into the portion that two (electricity) separates by second hole
Point.For example, the top layer can be made of graphene or can be including graphene and/or second hole narrow
Seam.In addition, second hole by the method for the type described above (that is, by applying self assembly resist) or can appoint
What its method produces.
The advantage of above equipment is that it can be manufactured with some or all of following characteristics：
It can have a large amount of holes, such as more than 1000, preferably more than 10,000, more preferably more than 100,
000.
It can have the hole for being arranged to high space density, and specifically high linear density, is greater than
Every cm 3-105A hole.By method of the invention, can in slit or groove with<The periodicity of 30nm puts hole interval
It sets, allow to connect all these holes and measures the electric current on each hole.
It can have the hole of size (diameter) less than 10nm, preferably less than 7nm, even more preferably less than 5nm.
Detailed description of the invention
According to embodiments described just below it will be evident that these and other aspects of the invention, and will be in conjunction with the implementation
Example illustrates these and other aspects.
In the following figure：
Fig. 1 shows the schematic plan to the first equipment according to the present invention；
Fig. 2 shows the sections that equipment shown in Fig. 1 is passed through along line II-II；
Fig. 3 shows the schematic plan to the second equipment according to the present invention, wherein several bottom slits with it is several
Top layer slit intersects；
Fig. 4 shows the section along line IV-IV across the equipment of Fig. 3；
Fig. 5 schematically shows the macromolecular for being assembled into the self assembly resist of layered pattern；
Fig. 6 schematically shows one of the self assembly resist and this resist that are assembled into cylindrical pattern
Molecule；
Fig. 7-12 schematically shows the continuous base that hole is generated in the single process layer for applying self assembly resist
This step；
Figure 13-24 schematically shows the consecutive steps for manufacturing equipment according to the present invention, including anti-by self assembly
It loses agent and generates graphene striped (Figure 13-17), these graphene stripeds (Figure 18-is vertically cut by self assembly resist
21), and by self assembly resist the hole across the substrate is generated as the last one step (Figure 22-24)；
Figure 25 schematically shows the perspective view of the equipment produced by process shown in Figure 13-24；
Figure 26-29 schematically shows the modification to manufacturing process shown in Figure 13-24, wherein against corrosion by self assembly
Agent generation is first step across the hole of the substrate；
Figure 30-38 schematically shows the consecutive steps for manufacturing equipment according to the present invention, including by optical lithography
It generates graphene striped (Figure 30), vertically cuts these graphene stripeds (Figure 31-34) by self assembly resist, and by
Self assembly resist generates the hole across the substrate as the last one step (Figure 32-38).
Similar Ref. No., or the number of integral multiple of difference 100 refer to the same or similar component in figure.
In addition, the right-hand side of Figure 13-24 and 26-38 all shows the top view of intermediate product, and the left-hand side of these figures is all shown
Along the cross-sectional view of corresponding dotted line.
Specific embodiment
2010/0327847 Al of US describes use of the graphene layer/electrode in nano-pore sequencing.In this patent,
Nano-pore is embedded into graphene by proposal, and several regions are remained with around the nano-pore.
It is well known, however, that graphene has high conductibility.It has reported in room temperature about 10,000cm2The mobility of/Vs
(K.S.Novoselov、A.K.Geim、S.V.Morozov、D.Jiang、Y.Zhang、S.V.Dubonos、
I.V.Grigorieva and A.A.Firsov, " Electric Field Effect in Atomically Thin Carbon
Films ", Science, 306 (204) 666-669).Therefore, the electric current in US2010/0327847 Al described device will not be by
Modulation is hardly modulated, and device has undesirable validity in terms of determining across the base of nano-pore, because almost
All electric currents will all pass through beside the nano-pore in remaining graphene.
In consideration of it, being seemed more effectively using nanometer gap, (H.W.Ch.Postma, " Rapid as proposed by Postma
Sequencing of individual DNA molecules in graphene nanogaps ", Nano Lett.10
(2010)420-425).As described in this paper, there are following additional advantages using nanometer gap, which obviate (nanometer) is electric
Pole snaps to the problem of nano-pore.
However, for practical purposes, the device tool that Postma is considered in its theoretical calculation is lacked there are two serious
Point：
In order to produce the device that can be easily manufactured, nanometer gap or " slit " must have across entire graphene
The finite length of electrode.This will be about 0.1-1 μm of size.Since single stranded DNA to be measured (ss-DNA) is great soft
Property, this will allow DNA to pass through a nanometer gap, especially folding mode in many ways.This will be destroyed with contemplated single base
The chance that resolution ratio measures.
The graphene layer does not have mechanical support, and although graphene is firm material, the device therefore manufactured
It will not be very firm.
The shunt current of the buffering liquid with ionic charge will be occurred through, which can flood times that will be measured
What tunnel current.
In order to handle these described problems, (graphene) device with crossed slot can be used.
Fig. 1 and 2 schematically depicts the example devices 100 designed according to aforementioned concepts.The central part of this equipment 100
Part is two layers, i.e.,：
" bottom " 110 including elongated the first slit of rectangle 111, width wb, and extends in the x-direction.
" top layer " 120 is set on aforementioned bottom 110, and part 120a, 120b that the top layer is disconnected by two are formed,
Described two parts are separated by the second slit 121, and the width of second slit is wt, and is extended in the y-direction.
First slit 111 and the second slit 121 are vertically oriented relative to each other, and in the middle part of the region of (rectangle) hole A
Divide ground overlapping, wherein unimolecule M may pass through the hole A.
As shown, equipment 100 further includes contact 130a, 130b, the contact is set to top layer portion 120a, 120b
On.Via these contacts, top layer is connected to circuit 140.This circuit 140 be suitable for sensing occur top layer portion 120a and 120b with
Electric reciprocation across the unimolecule of hole A.
It should be noted that setting is usually in the x-direction with the direction y with being up to wafer scale periodic heavy shown in Fig. 1 and 2
It is multiple, to generate separately addressable a large amount of hole A.
In addition, Fig. 3 and 4 shows the second equipment 200 with similar view, the equipment is analogous to the design of equipment 100
's.Only difference is that several (at this in several (being 4 herein) parallel slits 211 in bottom 210 and top layer 220
In be 3) vertical slits 221 intersect.Several slits can be respectively provided with identical width wt or wb, or be different
Width.If molecule M passes through one in the hole A that generates by this method, via the neighbouring part 220a of top layer 220,
220b or 220b, 220c or 220c, 220d sensing electric signals.
The device 100,200 for having the advantages that crossing nanotube slit, which has, is better than the following of known devices, to use stone
Black alkene nano-pore executes the sequencing based on transverse conductance：
It is open with the nanopore device structure proposed in 2010/0327847 Al of US on the contrary, only passing through nanometer in DNA
When just generate (tunneling) electric current.In addition, described device has the key advantage measured relative to zero background, that is,
It says, (very) limited signal is generated when no DNA passes through device, until no signal.
This apparatus structure can be easily manufactured, and ensure the single nanometer opening that only ss-DNA can be passed through.It need not
Nano-pore is made, but only two slits with nm width.
- ssDNA cannot pass through described device with folding mode, and folding mode will also prevent the detection of single base.
The equipment of mentioned kind needs to generate the hole or slit that width (wt, wb) is about several nm.For example, it is based on
The calculating that Postma (above-mentioned) executes tunnel current, needs the width of about 1-2nm.Such slit can pass through electron beam lithography
It generates, but this technology is unsatisfactory for the manufacture of the fast wafer grade of nano-pore sequencing device.It is desirable that related personnel
Optical lithography techniques will be used.However, current optical technology can not provide 1-2nm needed for manufacturing suitable nano slit
Width.
In order to solve this problem, in an embodiment of the present invention, it is proposed that come by using Self-Assembling of Block Copolymer in institute
Required hole (slit, nano-pore etc.) is made in the crossed slot device or other devices stated.Specifically, it is proposed that with three kinds
Mode is using Self-Assembling of Block Copolymer to carry out grapheme nano-pore sequencing：
With Self-Assembling of Block Copolymer to reduce narrow by electron beam or optical lithography (in the resist) production
Gap, or even further realize that (advantage of the method is to be suit best for in graphene to required nano-grade size
Nanometer gap on electrical isolation demand).
Reduce the size of the nano-pore made by optical lithography (in the resist).
It (in the resist) is made by electron beam lithography at where above-mentioned pre-fabricated patterns.
Block copolymer can be self-assembled into extremely regular pattern, with small to the intensive of about 5nm in length dimension
Feature (referring to Black et al., IBM J.Res.&Dev.2007,51 (5), 605).Most common block copolymer, diblock are total
Polymers is covalently joined together in a linear fashion made of two blocks of different types of copolymerization monomer.It is described
Self-Assembling of Block Copolymer process is to be pushed by the minimum of ionization energy, and it is mutual to depend on Flory-Huggins
Operational factors (for the measurement result of the unmixability of different blocks).Block copolymer can form many different phases, this master
To depend on the volume fraction of block.When being applied in film, spherical, cylindrical and stratiform is substantially only observed in the film
Phase.Self-assembly characteristic can be by allowing to send out between the surface characteristics (graphoepitaxy (grapho-epitaxy)) of prepatterned
Assembling is born to be aligned and guide.About the present invention, include by the Typical block copolymers used
PS-b-PMMA (poly- (styrene-b- methyl methacrylate)),
PS-b-PDMS (poly- (styrene-b- dimethyl siloxane)),
PS-b-PEO (poly- (styrene-b- ethylene oxide)),
PS-b-PVP (poly- (styrene-b-ethylene yl pyridines),
PMMA-b-PDMS (poly- (methyl methacrylate-b- dimethyl siloxane)),
PS-b-PI (poly- (styrene-block-isoprene),
Or form other block copolymers of self assembly pattern.
Fig. 5 schematically shows the layered pattern being self-assembly of by block copolymer macromolecular BCP.It is described big
Molecule BCP includes B block 1 and the alternate sequence of B2, wherein monomer composition of first B block 1 by the first kind, and the second block
B2 is by different Second Type monomer compositions.Different B blocks 1, the length of B2 (that is, quantity of contained monomer) can be it is identical or
Different.Macromolecular BCP has at least roughly the same space configuration, it means that it can be self-assembled into different macromoleculars
The equivalent block of BCP pattern closer to each other.In the example shown, it is respectively the striped of d1 and d2 that this, which causes generation to have width,
Or the layered pattern of " phase ".For example, such pattern can be 50%PS and the block copolymerization of 50%PMMA with volume fraction
Object generates.
Fig. 6 shows another self assembly pattern of block copolymer, wherein the pattern includes being embedded into the second phase B2
The first phase cylindrical body B1.For example, such pattern can use volume fraction be 30%PMMA (as the first phase B1) and
The block copolymer of 70%PS (as the second phase B2) generates.
Fig. 7-12 shows the schematic continuous basic step of manufacturing method according to the invention.
In Fig. 7, manufacturing method is to provide process layer 110 (or more generally referring to " PL ") beginning, for example, the place
Reason layer can be the non-conducting substrate of the equipment 100 of Fig. 1 and 2 (for example, SiO2)。
On the side of process layer 110, such as is deposited by optical lithography and patterned " main resist " 151.This
Patterning results in the wall of main resist 151, and the wall limits groove or channel in-between.
Fig. 8 shows next step, wherein self assembly resist 155 is deposited in former trenches.According to explaining above
The principle released, self assembly resist 155 have been self-assembled into the pattern of the first phase 155a and the second phase 155b.In the example shown,
The layered pattern being made of three stripeds extended in the y-direction is presented in the pattern.
In Fig. 9, the first phase 155a in the center of self assembly resist has been removed (such as passing through selective etch),
In the second phase 155b etch-resistance it is significantly higher compared with the first phase 155a.Correspondingly, it only remains with the second phase 155b
Parallel stripes composition pattern.
In different methods, the first phase 155a can be by the subsequent dissolution of photolytic degradation and catabolite by selectivity
Ground removes.For example, PMMA can in the case where being exposed to UV (for example, using light of 256nm) when ratio PS quickly degrade.This side
Method will be very suitably, because whole wafer can be disposably exposed to UV.There is no need to use high-resolution tool.
In Figure 10, the aforementioned residue of the second phase 155b has been used as exposure mask, passes through process layer described in the mask etch
110 to generate hole A, is slit in this case.Slit A can later serve as hole, and the hole wears unimolecule
It crosses.Alternately, be transferred in the hard mask layer of lower layer by the pattern that the aforementioned residue of the second phase is formed (for example,
Silica or silicon nitride), the hard mask layer is used subsequently to etching process layer 110 to generate hole A.
In fig. 11 it is shown that (selection) additional step, wherein having removed the residue 155b of self assembly resist
With main resist 151.Correspondingly, the process layer 110 with hole A is only left.However, if (for example) wanting process layer
On remaining resist be used as electrical isolation, then may also not use this step.
If Figure 12 shows the next step that produce the equipment 100 of Fig. 1 and 2.Then by top layer 120 (for example, being stone
Black alkene) it is deposited in the substrate 110 of structuring.In this top layer 120, then with the identical side of method shown in Fig. 7-10
Method generates hole or slit along the direction (that is, in the x-direction) of the hole A perpendicular to substrate 110, but is to make top layer 120 now
" process layer " carries out.
Although Fig. 7-11 shows the material circumstance in practice, wherein there is only one of the first phase of self assembly resist
Central fringer 155a, but it is also able to use multiple (three or more) stripeds by the first phase and the second phase composition in general, and/
Or the pattern using the cylindrical body in matrix, to generate several holes (slit, hole) parallel (for example, with reference to following FIG. 15-17
Or 22-24).For example, such method can be used for producing the equipment 200 of Fig. 3 and 4.
It should be noted that for each use of biosensor apparatus, it is necessary to disposably concurrently generate millions of
The nano-pore of meter uses so that the DNA of single diagnosis test is handled, because the DNA of individual cells is by 3x109A base composition
(if only genomic a part being sequenced, less nano-pore can use enough).
The manufacturing process is advantageous, because it allows using optical lithography.According to optical lithography techniques in 2011
Background, this technology can only make the feature of about 22nm size.However, the use of optical lithography will be reason for the angle of manufacture
Think.It has two key advantages better than electron beam lithography, i.e.,：
Whole wafer can disposably be irradiated (for example, patterning), cause to be so short that than the time needed for electron beam lithography
It is more, because in the case where electron beam lithography, it is necessary to individually inscribe each microgroove or pattern.
May lower production cost because optical lithography is that (and self assembly inherently comes traditional patterning techniques
Say to be also low cost process).
Since current optical lithography can not form required nano-scale patterns, above-mentioned proposal is by using block copolymerization
Object self assembly resist solves the problems, such as this.For example, the method in the equipment of above-mentioned (Fig. 1-4) type for forming
It is preferably, since it is desired that two vertical microgrooves for required nanometer gap.
In the experiment using self assembly resist, the PS-b-PMMA block copolymerization from toluene solution centrifugal casting is used
Object produces microgroove averagely with 9nm microgroove width.It is annealed in an oven with 200 DEG C to sample, to promote block copolymer
Self assembly.
Aforementioned pattern can be used as etched pattern, and to be etched in the dielectric layer of lower layer, the dielectric layer is for example
SiO2、SiNXOr Hexagonal boron nitride (h-BN, with graphene-structured tight fit).Then, it is carried out directly in graphene layer
Etching, because several seconds in oxygen-containing blood plasma are just enough to etch away graphene single or double layer.
In addition to above-mentioned slit generates, or alternatively, related personnel, which can be used, to be reduced through traditional light
Learn the technique (see below Figure 35-38) of (circle) nanoporous size being lithographically formed.In an experiment, total using different blocks
Copolymer mixture can be observed logical in standard resist layer inside the hole 65nm for generating acquisition by traditional optics
The nano-pore of 10-14nm size crossing Self-Assembling of Block Copolymer and being formed.
Although above description refers to using optical lithography, it is also feasible that electron beam lithography is used in prepatterned step
's.This will have the advantage for being better than the photoetching of conditional electronic beam, wherein broader pattern can be made, so that related personnel can more have
It works under the E-beam conditions of benefit.Self-Assembling of Block Copolymer may be used to make in required narrow gap.
Figure 13-24 shows another manufacturing process, wherein using different parameter and object by above-mentioned basic step (Fig. 7-
11) in triplicate.The right-hand side of Figure 13-24 all shows the top view of intermediate product, and the left-hand side of these figures is all shown
Along the cross-sectional view of corresponding dotted line.
In Figure 13, the process is to provide the beginning of the first process layer 320 (or " PL1 "), the first process layer setting
In in substrate 310.For example, substrate 310 can be Dielectric materials, such as SiO2, and the first process layer 320 is conduction
Property material, such as graphene single or double layer.
In Figure 14, (tradition) main resist 351 is deposited in the first process layer 320, and has been patterned or has tied
Structure, such as by optical lithography, to generate (width) groove in the y-direction.
Figure 15, which is shown, is deposited on self assembly resist 355 in the groove of main resist and is self-assembled into the first phase 355a
With the second alternate layer structure of phase 355b.
In Figure 16, the first phase 355a of self assembly resist has been removed, and only leaves second as etching mask
Phase 355b.The execution of this etching produces hole A1 (slit) in the first process layer 320.Correspondingly, this layer is divided now
At parallel stripes 320a, 320b, 320c, 320d and 320e.
In Figure 17, the remainder 355b of main resist 351 and (first) self assembly resist has been removed.In addition,
It should be pointed out that the sectional view of left-hand side has had rotated 90 ° relative to the cross-sectional view in earlier figures now.
For subsequent processing steps, (through prepatterned) graphene layer 320 will be considered as again under generating wherein
The process layer PL1 of one hole is perpendicular to the slit A2 of the first slit A1 in this case.
According to Figure 18, (second) main resist 352 is deposited on the top of aforementioned processing layer PL1, shown in it is against corrosion
Agent has been patterned, such as by optical lithography, to generate the groove perpendicular to prefabricated graphene striped.
In Figure 19, (second) self assembly resist 356 is deposited in former trenches, and is self-assembled into following figures
Case：A central fringer of first phase 356a is embedded between two stripeds of the second phase 356b.
In Figure 20, the first phase of self assembly resist has been removed, and the remaining phase 356b of resist has been used as covering
Film passes through the mask etch process layer 320.Resulting in narrow slit A2 in the x-direction, thus by the pre- of process layer
Striped processed is cut into two parts.
For subsequent processing steps, substrate 310 will be considered as in the process layer PL2 for wherein generating subsequent hole, at this
It is the hole A3 across substrate 310 in the case of kind.
According to fig. 21, this sub- process is started with removing previous self assembly resist residue 356b, is left main anti-
Agent 352 is lost, wherein the central groove of main resist 352 is in the x-direction.
Figure 22, which is shown, to be deposited (third) self assembly resist 357 and is self-assembled into following patterns：The circle of first phase
Cylinder 357a is embedded into the second phase 357b.
In Figure 23, the first phase of self assembly resist has been removed, and the remaining phase 357b of resist has been used as covering
Film passes through the mask etch substrate 310 (second processing layer).This results in a line round hole for penetrating substrate 310
Gap or hole A3.
Figure 24, which is shown, removes (second) main resist 352 and remaining (third) self assembly resist 357b in (optionally)
Resulting device 300 later.Described device can be subjected to further manufacturing step, for example, apply additional (for example, insulation) layer and/
Or it is connected to circuit (referring to Fig. 1-4).
Figure 25 shows the perspective schematic view of equipment 300 (size is not drawn on scale).It can be seen that, conductive graphite alkene
Parallel lines or a 320a-320e remain in substrate 310.These microgrooves are each cut into two parts, the part
It may be connected to circuit (not shown) and be located in the opposite side of (nanometer) hole or hole A3, wherein unimolecule M may pass through described
Hole or hole.In addition, the electrode obtained can each be placed in the microfluidic circuit of its own 320a-320e
(not shown).
Figure 26-29 schematically shows the modification of the above-mentioned manufacturing process relative to Figure 13-24.In this method, make
For first step rather than the last one step, the hole A3 for penetrating substrate 310 is generated by self assembly resist.
According to fig. 26, the process is opened so that main resist 353 is deposited in substrate 310 (and without graphene at top)
Begin, the substrate will be considered as the process layer PL1 of subsequent step.In addition, patterning main resist 353, such as pass through light
Photoetching is learned, to generate central groove in the x-direction.
Figure 27, which is shown, to be deposited self assembly resist 358 and is self-assembled into following patterns：The cylindrical body of first phase
358a is embedded into the second phase 358b.
In Figure 28, the first phase of self assembly resist has been removed, and the remaining phase 358b of resist has been used as covering
Film passes through the mask etch substrate 310 (process layer).This result in a line circular holes for penetrating substrate 310 or
Hole A3.
Figure 29, which is shown, is depositing to graphene layer 320 at the top of substrate 310 institute thus after coverage hole A3
State device.Present the step of can be similar to Figure 13-21, continues other manufactures, according to the step, first in graphene layer
It generates parallel stripes (utilizing slit A1), is then perpendicularly cut into two parts (using slit A2).With above-mentioned Figure 21 on the contrary,
Hole or hole A3 in substrate 310 have existed now, to allow to leap to the equipment 300 that Figure 24 is realized.
Figure 30-38 schematically shows the consecutive steps of the substitution manufacturing process of equipment 400.
This process is started with generating (width) striped by (for example) optical lithography in Figure 30 and in graphene layer 420.This
Graphene layer 420 is subsequent step " process layer " PL1.
According to Figure 31, main resist 451 is deposited on graphene layer 420, and and (for example) optical lithography
Patterning, to generate the central groove perpendicular to graphene striped.
Figure 32 shows next step, wherein depositing to self assembly resist 455 in former trenches, and self assembly
At the pattern of three stripeds, i.e., the first phase 455a and the second phase 455b that extend in the x-direction.
In Figure 33, the first phase of center of self assembly resist has been removed, and the remainder 455b of the second phase by
As exposure mask, by the mask etch process layer 420 to generate slit or hole A1.
According to Figure 34, the remainder 455b and main resist 451 of self assembly resist have been removed.This accomplishes by stone
Black alkene striped is vertically cut into two-part sub- process.
Next, the hole for penetrating substrate 410 must be generated.This is to deposit to other main resists 452 in Figure 35
Start on the graphene layer 420 of prepatterned.In addition, this main resist 452 is patterned to generate a line hole.
When using optical lithography for foregoing purpose, it may concurrently handle whole wafer and (illustrate only one in figure
Fraction).However, therefore these holes are relatively large, and need to be narrowed, for use in the expection of (for example) nano-pore sequencing
Using.
This, which narrows, starts from Figure 36, and self assembly resist 456 is deposited in prefabricated hole, and wherein this resist is from group
Dress up following patterns：The cylindrical body 456a of first phase is surround by the second phase 456b.
In Figure 37, the first phase of self assembly resist has been removed, and the remaining phase 456b of resist has been used as covering
Film passes through the mask etch substrate 410 (second processing layer PL2).This result in penetrate substrate 410 a line it is small
Circular holes or hole A3.
Figure 38 shows finally setting after (optionally) removes main resist 452 and remaining self assembly resist 456b
Standby 400.Equipment 400 has the parallel lines or 420a-420c of conductive graphite alkene, and wherein these microgrooves are each cut
At two parts, the part may be connected to circuit (not shown) and be located in the opposite side of (nanometer) hole or hole A3, wherein
Unimolecule M may pass through described hole or hole.Described device can be subjected to further manufacturing step, for example, apply it is additional (for example,
Insulation) it layer and/or is connected to circuit (referring to Fig. 1-4).Further, it is preferable to by electrode to 420a-420cIn be each placed into
In the microfluidic circuit of its own.
The process of mentioned kind is executed in an experiment.Silicon resin base bottom overleaf by local etching to 100nm or
Smaller thickness.The substrate is provided with graphene single or double layer.Resist is spun on the graphene layer, and described
The groove of 100nm-300nm is formed in resist layer.The trench fill has symmetrical block copolymer, is formed in annealing
Layered pattern.The graphene layer is optionally pre-processed using neutral oriented layer, to realize the vertical right of block copolymer
Together.Layered block copolymer patterns are used as etching resist exposure mask, and microgroove spacer patterns are transferred to graphene
In layer.Thereafter, remaining block copolymer and resist are peeled off from the substrate, and applies new resist layer.By perpendicular to
The optical lithography of first groove forms the new groove of groove width about 30nm-60nm.This trench fill has asymmetrical block total
Polymers is capable of forming cylindrical phase, wherein the cylindrical body is relative to the perpendicular orientation of substrate, and cylindrical body is positioned at graphite
On at the top of alkene microgroove.The graphene layer is optionally pre-processed using neutral oriented layer, to realize hanging down for block copolymer
Straight alignment (for example, can use brush polymer for this purpose, especially random brush copolymer, by gathering at random
The monomer A and B of conjunction and can be formed with end group that surface reacts).Equally, the block copolymer layer is used as etching to cover
Film, to be etched through graphene and across the substrate of lower layer.After the removing of remaining block copolymer, obtain with tiny
The nanohole array of Graphene electrodes.It then, can be by traditional semiconductor type processes step, using having 5nm under layer
Cr carrys out required contact and the rest part of producing device as the Au electrode of contact.Constructing these contact electrodes can easily make
It is completed with conventional lithography art.
As another embodiment of the present invention, it is proposed that do not remove resist or another protective layer (example at the top of graphene
Such as PMMA), or assign its optimum shape (such as taper).Which increase the slit heights at the top of graphene, to reduce ss-
DNA passes through the angle of the opening of the nanometer in crossed slot device.In addition, this also has following crucial sexual clorminances：It avoids and wears
The very big branch current of the cation buffer solution at the top of graphene layer is crossed, which will drown out any small buffer current.
In summary, the invention discloses the nanometer sequencing devices (solid nano hole) for using Self-Assembling of Block Copolymer
Manufacture, the especially manufacture of crossed slot nanometer sequencing device.The nanometer sequencing device can be specifically made of graphene layer.
Although being shown specifically and describing the present invention in attached drawing and preceding description, such diagram and explanation should be regarded
It is illustrative or exemplary rather than constrained；The present invention is not limited to the disclosed embodiments.According to attached drawing, disclosure
With the research of appended claims, those skilled in the art is appreciated that when practicing the advocated present invention and disclosed in implementing
Other versions of embodiment.In detail in the claims, word " comprising " is not precluded other element or steps, and indefinite hat
Word "a" or "an" is not precluded multiple.Certain measures are described in mutually different dependent claims does not indicate these
Measure can not be advantageously combined use.Any element symbol in detail in the claims is not considered limiting of its scope.
Claims (16)
1. method of the one kind for manufacturing the equipment (100,200,300,400) for handling unimolecule (M), the method includes
Following step：
A) " process layer " (PL, PL1, PL2) is provided；
B) self assembly resist (155,355,356,357,455,456) is deposited in the process layer, and makes its self assembly
At the pattern of two phases (155a, 155b, 355a, 355b, 356a, 356b, 357a, 357b, 455a, 455b, 456a, 456b)；
C) phase (155a, 355a, 356a, 357a, 455a, 456a) of the self assembly resist is selectively removed；
D) by the exposure mask of remaining self assembly resist (155b, 355b, 356b, 357b, 455b, 456b) in the process layer
At least one hole (A, Al, A2, A3) is generated in (PL, PL1, PL2)；
Wherein, step b), c) and d) the first process layer (PL1) and second processing layer (PL2) are performed twice respectively.
2. according to the method described in claim 1,
It is characterized in that, the method includes following additional steps：
E) remaining self assembly resist (155b, 355b, 356b, 357b, 455b, 456b) is removed.
3. according to the method described in claim 1,
It is characterized in that, the process layer (PL, PL1, PL2) the self assembly resist (155,355,356,357,455,
456) be pretreated before deposition, with influence resulting phase (155a, 155b, 355a, 355b, 356a, 356b, 357a,
357b, 455a, 455b, 456a, 456b) pattern.
4. according to the method described in claim 3,
It is characterized in that, the pretreatment includes the deposition and its pattern of main resist (151,351,352,353,451,452)
Change.
5. according to the method described in claim 1,
It is characterized in that, the second processing layer (PL2) includes first process layer (PL1).
6. according to the method described in claim 1,
It is characterized in that, apply in first time executes and second executes the self assembly resist (355,356,357,
455,456) pattern is in alignment and/or geometrically different.
7. according to the method described in claim 6,
It is characterized in that, each of described pattern all includes the striped of a phase, wherein the striped of different pattern inclines each other
Tiltedly.
8. according to the method described in claim 1,
It is characterized in that, the self assembly resist (155,355,356,357,455,456) includes block copolymer.
9. according to the method described in claim 1,
It is characterized in that, the process layer includes non-conducting sublayer (110,210,310,410) or material and/or conduction temper
Layer (120,220,320,420) or material.
10. according to the method described in claim 9,
It is characterized in that, the conductibility sublayer (120,220,320,420) or material include graphene or are derived by graphene
Material.
11. according to the method described in claim 1,
It is characterized in that, additional layer is at least partially deposited on the process layer (PL, PL1, PL2).
12. according to the method described in claim 1,
It is characterized in that, the process layer (PL, PL1, PL2) is connected to circuit (140), it can control and wear by the circuit
Cross the reciprocation of the molecule (M) of the hole (A, Al, A2, A3).
13. according to the method described in claim 4,
It is characterized in that, the patterning of main resist (151,351,352,353,451,452) passes through optical lithography and/or electronics
Beam photoetching carries out.
14. according to the method described in claim 10,
It is characterized in that, the graphene or the material as derived from graphene are present in the single layer less than five.
15. according to the method described in claim 10,
It is characterized in that, the graphene or the material as derived from graphene are present in a single layer.
16. according to the method for claim 11,
It is characterized in that, the additional layer is non-conductive additional layer.
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| EP12174261.3A EP2642341A2 (en) | 2012-03-22 | 2012-06-29 | Manufacturing method of an apparatus for the processing of single molecules |
| PCT/IB2013/052026 WO2013140316A2 (en) | 2012-03-22 | 2013-03-14 | Manufacturing method of an apparatus for the processing of single molecules |
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| KR101489154B1 (en) * | 2014-06-26 | 2015-02-03 | 국민대학교산학협력단 | Method for manufacturing nanogap sensor using residual stress and nanogap sensor manufactured thereby |
| US10961563B1 (en) * | 2019-12-19 | 2021-03-30 | Robert Bosch Gmbh | Nanoscale topography system for use in DNA sequencing and method for fabrication thereof |
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| US8734904B2 (en) * | 2010-11-30 | 2014-05-27 | International Business Machines Corporation | Methods of forming topographical features using segregating polymer mixtures |
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| EP2828707A2 (en) | 2015-01-28 |
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